Silicone compositions containing acrylate cure accelerator

ABSTRACT

Compositions are disclosed which include between about 0.05 to about 5 or less wt. % of at least one acrylate monomer based on the total weight of the composition. The acrylate monomer reduces the peak cure temperature, thereby accelerating the rate of cure, without sacrificing completeness of the cure or the release performance of the cured product. The addition of the acrylate monomer also enables a reduction in the amount of costly platinum catalyst required to effectively cure a composition. In addition to the acrylate monomer, the compositions also include a silicone base polymer, a crosslinking agent, and platinum catalyst. The cured compositions exhibit properties useful for incorporation into release liners, adhesive articles, medical products and gaskets.

This application claims the benefit of U.S. provisional application Ser.No. 62/869,720 filed Jul. 2, 2019, the contents of which areincorporated herein in their entirety by reference.

TECHNICAL FIELD

The present disclosure relates to compositions including silicone basepolymers and an acrylate cure accelerator, which can be present at about5 or less wt. % based on the total weight of the composition. Theacrylate cure accelerator (e.g., an acrylate monomer) beneficiallyreduces the peak cure temperature of the composition, therebyaccelerating the rate and time of cure, and further reduces the amountof catalyst needed for initiating an effective cure, for example, 90% ormore. The present disclosure also relates to the addition of one or moreO-vinyl compounds to silicone-containing compositions that are usefulfor adhesive liners and release products such that the acrylate cureaccelerators and O-vinyl compounds synergistically operate to accelerateand enhance the completeness of cure, reduction of peak cure temperatureand amount of catalyst needed for initiating an effective cure. Thecompositions can be used as a material having desirable releaseproperties, for example, release liner coatings, silicone elastomers formedical devices, silicone elastomers for gaskets, and as siliconeelastomers for other molded articles.

BACKGROUND

Silicone resins impart elastic, low surface energies, and are thereforedesirable for use in the adhesive industry. Notably, silicone-basedcompositions such as a coating are capable of holding a substrate (e.g.,a label) in place for storage and transport, and they also enable simpleand quick detachment of a substrate from a release liner. Traditionalcomponents of compositions for use as a coating include silicone,crosslinking agents, and catalysts, including, for example, platinumcatalysts. However, the high costs associated with using platinumcatalysts have prompted the adhesive industry to investigate affordablealternatives. Little success has been achieved in decreasing the amountof platinum catalyst needed to successfully cure compositions containingsilicone, for at least the reason that decreasing the amount of platinumcatalyst can lead to insufficient curing and/or a slower cure rate.

DESCRIPTION OF THE FIGURES

FIG. 1 shows an example relationship between the concentration of theacrylate monomer EOEOEA in parts per hundred (pph) and the peak curetemperature (° C.) for silicone base compositions containing 10 ppm, 20ppm and 30 parts per million (ppm) of platinum catalyst.

FIG. 2 . shows an example relationship between the concentration of theacrylate monomer EOEOEA in parts per hundred (pph) and the peak width indegrees Celsius (° C.) for silicone base compositions containing 10 ppm,20 ppm and 30 ppm of platinum catalyst.

FIG. 3 shows an example relationship between the concentration of theacrylate monomer ODA in parts per hundred (pph) and the peak curetemperature in degrees Celsius (° C.) for a silicone base compositioncontaining 35 parts per million (ppm) of platinum catalyst.

FIG. 4 shows an example relationship between the concentration of theacrylate monomer Tego RC722 in parts per hundred (pph) and the peak curetemperature in degrees Celsius (° C.) for a silicone base compositioncontaining 35 ppm of platinum catalyst.

FIG. 5 shows an example relationship between storage modulus in Pascals(Pa) and the cure temperature in degrees Celsius (° C.) for siliconebase compositions containing no additives, an acrylate monomer (TMPTA),and an acrylate monomer/O-vinyl compound blend (TMPTA/BDVE).

SUMMARY

In light of the above, there is a need for a release coating compositionthat cures quickly without the large amounts of expensive platinumcatalyst currently required to initiate and drive the cure of siliconecompositions to completion. The present specification describescompositions that cure quickly to completion with reduced amounts ofcatalyst (e.g., platinum), while also withstanding the rigors of hightemperature/high speed processing. The present specification describessilicone-containing compositions containing the conventional amounts ofcatalyst, but which cure faster at significantly lower temperatures thanare currently known in the art. The present specification also describescompositions that may be provided as a coating on liners. Thecompositions are capable of rapidly curing to form a liner coating thatwill hold substrates (e.g., labels) in place for storage and transport,while also enabling simple and quick substrate detachment from a releaseliner. Additionally, the present specification also describescompositions that may be provided on liners and incorporated intoadhesive articles, such as label sheets. These compositions solve theproblem of reducing the costs associated with the use of expensivecatalysts and running ovens at high temperatures, while alsoaccelerating the cure of said compositions without sacrificing thecompleteness of cure, which might lead to reduced bonding quality, orpossible debonding, between the composition and the adhesive on asubstrate of the adhesive article.

In a first aspect, disclosed is a composition that includes a siliconebase polymer and a cure accelerator that is an acrylate monomer presentin the composition from about 0.05 to about 5 weight percent (wt. %)based on the total weight of the composition.

In an example of aspect 1, the silicone base polymer is a vinylfunctional silicone base polymer.

In another example of aspect 1, the silicone base polymer is presentfrom between about 50 wt. % to about 95 wt. % of the total weight of thecomposition.

In another example of aspect 1, the composition is uncured.

In another example of aspect 1, the composition further includes anO-vinyl ether compound, for example, 1,4 cyclohexanedimethanol divinylether, butanedioldivinylether (BDVE), and dodecylvinylether (DDVE).

In another example of aspect 1, the O-vinyl ether compound is presentfrom between about 0.01 wt. % to about 10 wt. % of the total weight ofthe composition.

In another example of aspect 1, the acrylate monomer is selected fromthe group of a mono-, di-, tri-, or multifunctional acrylate monomer.

In another example of aspect 1, the acrylate monomer is selected fromthe group of hexanediol diacrylate, tricyclodecanediol diacrylate,isobornyl acrylate, octyl/decyl acrylate, silicone diacrylate, siliconehexaacrylate, Tego RC722, 3-acryloxypropyl trimethoxysilane, andtrimethylolpropane triacrylate.

In another example of aspect 1, the acrylate monomer is present frombetween about 0.05 wt. % to about 2 wt. % of the total weight of thecomposition or from between about 0.05 wt. % to about 1 wt. % of thetotal weight of the composition. In another example of aspect 1, theacrylate monomer is present from between about 0.1 wt. % to about 2 wt.% of the total weight of the composition or from between about 0.1 wt. %to about 1 wt. % of the total weight of the composition.

In another example of aspect 1, the acrylate monomer is a hydrophilicacrylate monomer, for instance, an acrylate monomer having a hydrophilicside chain or group containing less than twelve carbons (C12).

In another example of aspect 1, the composition further includes acrosslinking agent having a silicon hydride functional group.

In another example of aspect 1, the composition further includes acontrolled release agent (CRA).

In another example of aspect 1, the controlled release agent is presentin an amount of about less than 50 wt. % of the total weight of thecomposition, for example, between about 4 wt. % and about 12 wt. %.

In another example of aspect 1, the composition further includes acatalyst, for example, a catalyst that includes platinum.

In another example of aspect 1, the catalyst is present in the range ofbetween about 10 ppm to about 100 ppm, or 35 ppm or less based on thetotal weight of the composition.

In a second aspect, the composition of aspect 1 is exposed to atemperature in the range of about 70° C. to about 140° C. for a timeperiod in the range of about 1 second to about 10 seconds such that thecomposition is cured 90% or more, for example, 95% or more. In anotherexample, the composition of aspect 1 is exposed to a temperature in therange of about 70° C. to about 140° C. for a time period in the range ofabout 5 seconds to about 40 seconds such that the composition is cured90% or more, for example, 95% or more.

In an example of aspect 2, the time period for curing the composition isin the range of about 1 second to about 5 seconds, or 5 seconds or less.In another example, the time period for curing the composition is in therange of about 10 seconds to about 40 seconds, or 40 seconds or less.

In another example of aspect 2, the temperature for curing thecomposition is in the range of about 100° C. to about 130° C.

In another example of aspect 2, the modulus (G′) of the compositionafter curing is 1×10⁶ Pascals or more measured at a temperature of about120° C.

In another example of aspect 2, the loss factor (tan δ) of thecomposition after curing is less than 0.01 measured at a temperature ofabout 120° C.

In another example of aspect 2, the cured composition is a releasematerial, for example, a coating on a liner, an elastomer for a medicaldevice, or an elastomer for a gasket.

In a third aspect, there is a release liner that includes the curedcomposition of aspect 1 and a liner that has a first surface and asecond surface, wherein the cured composition is disposed as a coatingon a portion of the first surface of the liner.

In an example of aspect 3, the liner is selected from the group of aplastic or polymeric film, paper, and coated paper.

In a fourth aspect, there is an adhesive article that includes asubstrate, an adhesive disposed on a surface of the substrate, and arelease liner having a liner with a first surface and a second surface,a portion of the first surface having the cured composition of aspect 1disposed thereon and in contact with the adhesive.

In an example of aspect 4, the substrate is a film, paper, or acombination thereof.

In another example of aspect 4, the adhesive is a pressure sensitiveadhesive.

In another example of aspect 4, the liner is a plastic or polymericfilm, paper or a coated paper.

Any one of the above aspects (or examples of those aspects) may beprovided alone or in combination with any one or more of the examples ofthat aspect discussed above; e.g., the first aspect may be providedalone or in combination with any one or more of the examples of thefirst aspect discussed above; and the second aspect may be providedalone or in combination with any one or more of the examples of thesecond aspect discussed above; and so-forth.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from that description or recognized by practicing theembodiments as described herein, including the detailed descriptionwhich follows, the claims, as well as the appended figures.

It is to be understood that both the foregoing general description andthe following detailed description are merely exemplary, and areintended to provide an overview or framework to understanding the natureand character of the claims. The accompanying figures are included toprovide a further understanding, and are incorporated in and constitutea part of this specification. The figures illustrate one or moreembodiments, and together with the description serve to explainprinciples and operation of the various embodiments.

DETAILED DESCRIPTION

The terminology as set forth herein is for description of theembodiments only and should not be construed as limiting the inventionas a whole. Herein, when a range such as 5-25 (or 5 to 25) is given,this means preferably at least or more than 5 and, separately andindependently, preferably not more than or less than 25. In an example,such a range defines separately and independently 5 or more, andseparately and independently, 25 or less.

As used herein, the term “about” means that amounts, sizes,formulations, parameters, and other quantities and characteristics arenot and need not be exact, but may be approximate and/or larger orsmaller, as desired, reflecting tolerances, conversion factors, roundingoff, measurement error and the like, and other factors. When the term“about” is used in describing a value or an end-point of a range, thedisclosure should be understood to include the specific value orend-point referred to. Whether or not a numerical value or end-point ofa range in the specification recites “about,” the numerical value orend-point of a range is intended to include two embodiments: onemodified by “about,” and one not modified by “about.” It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint.

The terms “substantial,” “substantially,” and variations thereof as usedherein are intended to note that a described feature is equal orapproximately equal to a value or description. For example, a“substantially planar” surface is intended to denote a surface that isplanar or approximately planar. Moreover, “substantially” is intended todenote that two values are equal or approximately equal. In someembodiments, “substantially” may denote values within about 10% of eachother, for example within about 5% of each other, or within about 2% ofeach other.

It is noted that the terms “substantially” and “about” may be utilizedherein to represent the inherent degree of uncertainty that may beattributed to any quantitative comparison, value, measurement, or otherrepresentation. These terms are also utilized herein to represent thedegree by which a quantitative representation may vary from a statedreference without resulting in a change in the basic function of thesubject matter at issue.

Provided are compositions containing silicone and incorporating betweenabout 0.05 to about 5 or less wt. % of an acrylate cure accelerator(e.g., acrylate monomer) based on the total weight of the composition.The addition of one or more acrylate cure accelerators in these amountsto compositions including silicone base polymers, catalyst and across-linker desirably reduces the peak cure temperature of thecomposition, thereby accelerating the rate and time of cure. It has alsobeen surprisingly found that the addition of acrylate cure acceleratorin these amounts selectively enables a reduction in the amount ofcatalyst (e.g., a platinum-based catalyst) needed to initiate cure thecomposition to effective completion without sacrificing the completenessof cure or having detrimental effects on release properties of the curedsilicone composition. The compositions provided for herein areespecially useful in release liners, particularly for adhesive articles.

Composition Materials

The curable compositions of the present disclosure include one or moresilicone base polymers such that the compositions are siliconecompositions. The compositions further include one or more acrylatemonomers as a cure accelerator, one or more catalysts, and one or morecrosslinking agents. Optionally, in some embodiments, the compositionsmay additionally include one or more O-vinyl compounds and a controlledrelease agent as described herein.

Generally, the one or more silicone base polymers of the compositionspossess reactive vinyl groups. In one or more embodiments, the siliconebase polymer is a vinyl functional silicone base polymer or siloxane,for example, a diorganopolysiloxane or a dialkylpolysiloxane. In oneexample, the silicone base polymer is a multifunctional polymer that hasvinyl groups along the polymer chain, and/or vinyl groups at theterminal ends of the chain. In another example, the silicone basepolymer can be polydimethylsiloxane (PDMS) or derivative thereof. Vinylterminated PDMS is an example silicone base polymer. Exemplary siliconebase polymers for use in the present disclosure include, but are notlimited to, Wacker Dehesive 915 and Dowsil SL161. The total amount ofsilicone base polymer (e.g., one or more silicone polymers) can bepresent in a range of from about 50 wt. % to about 95 wt. % or about 60wt. % to about 90 wt. % of the total weight of the composition. Inanother example, the composition contains about 50 wt. % or more, about60 wt. % or more, about 65 wt. % or more, about 70 wt. % or more, orabout 75 wt. % or more of total silicone base polymer based on the totalweight of the composition, for instance, the uncured composition. Inanother example, the composition can contain about 95 wt. % or less,about 90 wt. % or less, about 85 wt. % or less or about 80 wt. % or lessof the total amount of silicone base polymer.

The acrylate cure accelerators such as acrylate monomers of thecompositions function to effectively and beneficially reduce the peakcure temperature of the composition, thereby providing a lower curetemperature needed and accelerating the rate and time of cure. The term“acrylate” herein to define acrylate cure accelerator specificallyrefers to acrylates, and not to methacrylates, or combinations ofacrylates and methacrylates. In certain embodiments, the acrylate cureaccelerator is hydrophilic, and includes a hydrophilic side chain orgroup containing less than twelve carbons (C12). The acrylate cureaccelerator may be present in an amount between about 0.05 wt. % toabout 5 wt. % based on the total weight of the composition. In anotherexample, the acrylate cure accelerator is present in a range of about0.1 wt. % to about 5 wt. %, of about 0.15 wt. % or more, about 0.2 wt. %or more or about 0.25 wt. % or more based on the total weight of thecomposition. In another example, the composition can contain about 4.5wt. % or less, about 4 wt. % or less, about 3.5 wt. % or less or about 3wt. % or less of acrylate cure accelerator. In one or more embodiments,the curable composition contains about 5 wt. % or less of total acrylatecure accelerator to ensure a high modulus cured composition is formed.In another example, the composition (e.g., in an uncured state) caninclude acrylate cure accelerator in a range of about 0.1 to about 10pph (parts of acrylate cure accelerator per hundred parts of siliconebase polymer present in the composition), about 0.2 to about 5 pph,about 0.25 to 5 pph, about 0.2 to about 2 pph, or about 0.5 pph, about0.75 pph, about 1 pph, about 1.25 pph, about 1.5 pph or about 1.75 pph.In another example, the composition can contain about 10 pph or less,about 5 pph or less, about 4 pph or less, about 3 pph or less or about 2pph or less of total acrylate cure accelerator. In yet another example,the composition can include up to about 0.1 pph, about 0.2 pph, about0.25 pph, about 0.5 pph, about 1 pph, about 1.5 pph, about 2 pph, orabout 5 pph of total acrylate cure accelerator.

In one or more embodiments, the one or more acrylate cure acceleratorsare acrylate monomers that are a mono-functional acrylate monomer. Inother embodiments, the one or more acrylate monomers are di-, tri-, ormulti-functional. Exemplary acrylate monomers for use in the presentinvention include, but are not limited to, hexane diol diacrylate(HDDA), tricyclodecanediol diacrylate, isobornyl acrylate, octyl/decylacrylate, silicone diacrylate, silicone hexaacrylate, Tego RC722,3-acryloxypropyl trimethoxysilane, trimethylolpropane triacrylate(TMPTA), isodecyl acrylate (IDA), propoxylated (3 mol) TMPTA,ethoxylated (3 mol) TMPTA, 2-ethoxyethoxy ethyl acrylate (EOEOEA),propoxylated 2 neopentyl glycol diacrylate (PONPGDA), 2-phenoxyethylacrylate, ethoxylated (15 mol) TMPTA, polyethylene glycol 200 diacrylate(PEG200DA).

The compositions disclosed herein will also contain a crosslinking agentor crosslinker, for example, a silicon hydride agent. A wide array ofcrosslinking agents may be used in the disclosed composition, forexample, a polyorganohydrosiloxane crosslinking agent as known.Crosslinking agents having silicon hydride functional groups, Si—Hgroups, are particularly preferred. Exemplary crosslinking agents foruse in the present invention include, but are not limited to, V90,available through Wacker Chemical, and Syl-Off 7488, available throughDow Chemical Corporation. The crosslinking agent may be present in arange between about 1 wt. % to about 15 wt. % based on the total weightof the composition. In another example, the crosslinking agent ispresent in a range of about 2 wt. % to about 14 wt. %, of about 3 wt. %or more, about 4 wt. % or more or about 5 wt. % or more based on thetotal weight of the composition. In another example, the composition cancontain about 14 wt. % or less, about 13 wt. % or less or about 12 wt. %or less of crosslinking agent.

The compositions disclosed herein also include a catalyst, for example,a metal-based catalyst such as platinum or rhodium. A variety ofcatalysts may be used in the composition. Platinum- (Pt) containingcatalysts, such platinum, a platinum complex or platinum compound, arepreferred for use in the compositions. In one or more embodiments, theplatinum catalyst is Karstedt's catalyst, an organoplatinum compoundderived from divinyl-containing disiloxane, which is suitable inhydrosilylation reactions.

Compositions often employ greater than 40 ppm of platinum catalysts.Less than 40 ppm of platinum catalyst can undesirably lead to anincomplete curing and compromised bonding with adhesive-coatedsubstrates when compositions are used in a release application. However,in preferred embodiments of the compositions disclosed herein, thecatalyst is present in an amount of between about 5 ppm to about 100ppm, about 10 ppm to about 80 ppm, or about 15 ppm to about 60 ppm ofthe total weight of the composition. In some embodiments, the catalyst(e.g., a platinum-based catalyst) constitutes about 40 ppm or less,about 35 ppm or less, about 30 ppm or less, about 25 ppm or less orabout 20 ppm or less of the total weight of the composition. In one ormore embodiments, the amount of platinum catalyst may be within a rangeof about 1 ppm to about 20 ppm of the total weight of the composition.In other embodiments, the amount of platinum catalyst may be within arange of about 5 ppm to about 10 ppm of the total weight of thecomposition.

In one or more embodiments of the compositions, the compositions alsooptionally include an O-vinyl compound. A wide array of O-vinylcompounds may be used in the composition. For example, O-vinyl ethercompounds may be used. In one or more embodiments, the O-vinyl ethercompound is selected from 1,4 cyclohexanedimethanol divinyl ether,butanedioldivinylether (BDVE), and dodecylvinylether (DDVE). The O-vinylcompound may be present in a range between about 0.01 or 0.05 wt. % toabout 5 or less wt. % or about 0.1 wt. % to about 3 wt. % based on thetotal weight of the composition. In one or more embodiments, the O-vinylcompound is present at about 2.5 wt. % or less, about 2 wt. % or less,about 1 wt. % or less or about 0.5 wt. % or less of the total weight ofthe composition.

In another embodiment of the composition, the composition also includesa controlled release agent (CRA). When added to the composition,controlled release agents function to adjust the binding strength of thecomposition, for example, when used as an adhesive article. In one ormore embodiments, controlled release agents include silicone resinscomprising monovalent (M) siloxane groups (R₃SiO_(1/2) groups), whereinR is a monovalent hydrocarbon group that is typically methyl or vinyl,and tetravalent (Q) siloxane groups (SiO_(4/2) groups) only, otherwiseknown as MQ resins. The vinyl groups allow the CRA to react with thesilicone polymer during cure. In one or more embodiments, the controlledrelease agent may be CRA 17 available from Wacker or SL 40 supplied byDow Chemical. The controlled release agent may be present in an amountless than 50 wt. % of the total weight of the composition. In otherembodiments, the controlled release agent may be present in a rangebetween about 1 wt. % to about 35 or less wt. %, about 2 wt. % to about25 or less wt. %, or about 4 wt. % to about 12 or less wt. % based onthe total weight of the composition.

Exemplary compositions in accordance with the present disclosure are setforth in Table 1 below:

TABLE 1 Exemplary Composition Materials Component Amount (wt. %)Silicone Base Polymer(s) 50-95 Catalyst(s) As Noted CrosslinkingAgent(s)  4-12 Acrylate Cure Accelerator(s) 0.05-5   O-Vinyl Ether(s) AsNoted Controlled Release Agent(s) As Noted

Preparation of the Composition

The following is an exemplary method of preparing a composition. Thesilicone base polymer, crosslinking agent, catalyst and, optionally, thecontrolled release agent are added together, and the components aremixed together, for example, for about 5 to about 25 minutes or untilthoroughly mixed, to prepare a mixture. The acrylate cure acceleratorand, optionally, the O-vinyl ether compound are added to the mixture andfurther mixed (e.g., for about 5 to about 25 minutes) to form a reactivemixture. In one or more embodiments, the step of adding the acrylatecure accelerator, and optionally the O-vinyl ether compound, to thecomponents of the mixture in the method of preparing a curable (e.g.,heat curable) composition is performed immediately before application toa curing condition, for example, heating the composition.

In one or more embodiments, the silicone base polymer and crosslinkercan be combined together and mixed until a uniform blend is achievedbefore adding an optional controlled release agent. The blend is furthermixed or agitated until uniform. A catalyst is further added, forinstance in the form of a solution, such as a platinum-containingsolution, and mixed to form a mixture. The acrylate cure acceleratorand, optionally, the O-vinyl ether compound are added to the mixture andfurther mixed (e.g., for about 5 to about 25 minutes) to form a reactivemixture. The reactive mixture is subjected to a curing condition, forexample, heating the composition. Heating can be achieved by anysuitable means, for example, in an oven.

Curing conditions for the composition can include exposing thecomposition to heat. In an example, the composition is heated in an ovenor series of ovens to initiate curing. The ovens can be pre-heated at arange of about 130° C. to about 150° C. in order to effectuate curing.However, it has been found that the compositions disclosed herein can becured about 90% or more or about 95% or more when the compositions areheated at a range of about 70° C. to about 140° C., about 75° C. toabout 130° C., or about 80° C. to about 120° C. In one or moreembodiments, the coating compositions can be cured at about 90% or moreor about 95% or more when the compositions are heated at a range ofabout 70° C. to about 120° C., about 75° C. to about 115° C., or about80° C. to about 110° C. In other embodiments, the compositions can becured about 90% or more or about 95% or more at higher temperatures, forexample, at a range of about 120° C. to about 180° C., about 125° C. toabout 170° C., or about 130° C. to about 160° C., or at about 140° C. or150° C.

As evidenced in the Examples below, the use of the acrylate cureaccelerator can reduce the peak cure temperature of the compositions,for example, at a range of about 70° C. to about 140° C., about 75° C.to about 135° C., about 80° C. to about 130° C. or about 90° C., about100° C., about 110° C., or about 120° C. Curing conditions, such as theexposure temperature for the compositions, can be adjusted accordingly.For instance, oven temperatures can be set below typical curetemperatures with the use of the acrylate cure accelerators. TheExamples also exhibit the cure temperature for achieving a cure of 95%or more, for example, at a range of about 70° C. to about 140° C., about75° C. to about 135° C., about 80° C. to about 130° C. or about 90° C.,about 100° C., about 110° C., or about 120° C.

The compositions also benefit from use of the acrylate cure acceleratorsin that the amount of time, for example dwell time in heated conditionssuch as an oven, to achieve effective cure (e.g., 90% or 95% or more) isreduced. In one or more embodiments, the compositions can be cured for atime period of about 1 second to about 1 minute, about 2 seconds toabout 45 seconds, about 3 seconds to about 30 seconds, about 25 secondsor less, about 20 seconds or less, about 15 seconds or less, about 10seconds or less, about 8 seconds or less, or about 5 seconds or less ata temperature in the range of about 70° C. to about 130° C., about 75°C. to about 125° C., or about 80° C. to about 120° C. In otherembodiments, higher cure temperatures can be used with the same curetime periods as above, for instance, at a range of about 120° C. toabout 180° C., about 125° C. to about 170° C., or about 130° C. to about160° C., or at about 140° C. or 150° C. Curing time periods for curingthe composition can be in the range of 10 seconds to 40 seconds or morein examples when both the composition is to be cured and simultaneouslydrying adhesive material of an adhesive article as described herein. Inone or more embodiments, the composition can be applied as an uncuredcoating on a first surface of a liner substrate of a release liner. Therelease liner with the composition coating can be positioned on asubstrate (e.g., a label that may be made of a polymeric film, paper, orcombinations thereof) that is at least partially covered with a thinlayer of an adhesive that may be pressure sensitive. The compositioncoating of the release liner can be in direct contact with the adhesiveon the substrate such that the adhesive layer is disposed between thesubstrate and the coating composition on the liner material of therelease liner. The article can be heated, for example in an oven atconditions described above, to both cure the composition of the releaseliner and dry the adhesive on the substrate, for instance, by exposingthe article for a time period of about 10 seconds to about 40 seconds or1 minute at a temperature in the range of about 70° C. to about 130° C.,about 75° C. to about 125° C., or about 80° C. to about 120° C.

Release Liners

The present disclosure also provides for the use of applying thecomposition to coat a flexible liner that can be used to form a releaseliner. The release liner functions as a carrier for, and which protects,a substrate (e.g., label). The composition disclosed herein is typicallyapplied as a very thin release layer or coating (e.g., about 1 μm,micron) to the surface of the flexible liner. The thickness of therelease layer of the composition can be in the range of about 0.05 toabout 3 μm, about 0.1 to about 2 μm, about 0.25 to about 1 μm, or about0.5, about 0.75, about 1, about 1.5 or about 2 μm. Applying a releaselayer of the composition to a surface of a liner provides for an elasticand low-energy layer that holds a label in place on the surface of aliner during storage, and also provides for quick and simple removal.

In some embodiments, the flexible liner for coating with the compositionmay be a polymeric film, a paper material, and/or a coated papermaterial. A variety of materials can be used for the flexible linerincluding, but not limited to, conventional smooth surface papermaterials, polyester and polyolefin films. In certain embodiments, theflexible liner coated with the composition (i.e. release liner) is ofadequate thickness to strengthen a backing sheet. In a preferredembodiment, the release liner possesses enough rigidity and/or thicknessto maintain a flat configuration, while also having enough flexibilityto bend in response to an external stimulus.

In order to prevent the silicone polymer from transferring to anadhesive and interfering with the adhesion of an adhesive article, suchas a label, the composition coated on the flexible liner must becrosslinked through a process known as curing. Uncured silicone in thecomposition is undesirable because it may interfere with printing andother label processing steps.

Once the composition for coating a flexible liner is prepared, asdisclosed above, it is applied to the flexible liner using a series ofrollers. The rollers mash and form the composition reactive mixture intoa thin layer at thicknesses noted above onto the flexible liner. Thecoated release liner is then heated, for example, in an oven or seriesof ovens to initiate curing of the reactive mixture. Typically, theovens are heated at a range of about 130° C. to about 150° C. in orderto effectuate curing. However, it has been found that the release linercoating composition disclosed herein can be cured about 90% or more orabout 95% or more when the ovens are also heated at temperatures below130° C., for instance, at a range of about 70° C. to about 130° C.,about 75° C. to about 125° C., or about 80° C. to about 120° C. In oneor more embodiments, the compositions coated on a flexible liner can becured at about 90% or more or about 95% or more when the compositionsare heated at a range of about 70° C. to about 120° C., about 75° C. toabout 115° C., or about 80° C. to about 110° C.

In one example, the coated flexible liner is moved through the ovens atapproximately 2,000 feet per minute, such that the time exposed toelevated temperatures at which curing occurs is between about 1 secondto about 5 or 10 seconds. In some embodiments, the time at which curingoccurs is in the range of 1 to 5 seconds, or about 2, 3 or 4 seconds.During curing, the vinyl groups of the silicone react with the siliconhydride groups of the crosslinking agent through a process calledhydrosilylation. The resulting product is a highly crosslinked, threedimensional polymer. The curing process does not produce any volatilebyproducts. Little or no post-curing occurs once the liner exits theovens and is returned to room temperature. In one or more embodiments,the compositions can be cured for a time period of about 1 second toabout 30 seconds, about 2 seconds to about 25 seconds, about 20 secondsor less, about 15 seconds or less, about 10 seconds or less or about 5seconds or less at a temperature in the range of about 70° C. to about140° C., about 75° C. to about 130° C., or about 80° C. to about 120° C.

The hydrosilylation that occurs during silicone cure is an exothermicprocess that produces an exothermic peak, which is measured usingdifferential scanning calorimetry (DSC). DSC is an industry-recognizedmethod of analyzing the difference in the amount of heat required toincrease the temperature of a sample compared to a reference, and ismeasured as a function of temperature. Typically, the temperature isincreased at 10° C. per minute. Heat flow is typically measured inwatts.

Several measurements of the exothermic peak provide informationregarding the overall cure. Peak temperature, generally measured indegrees Celsius (° C.), is the temperature where the exothermic peakreaches its maximum. Peak area, generally measured in Joules per gram(J/g), measures the total exotherm and is a measure of the completenessof the cure. Generally, a greater peak area figure indicates a morecomplete the cure. Peak width, generally measured in degrees Celsius (°C.), measures the speed at which cure occurs. Peak height, generallymeasured in Watts per gram (W/g), indicates the degree (intensity) ofcure. A narrow and high exothermic peak indicates a fast, intense cure,while a short and wide exothermic peak indicates a slow, gradual cure ofthe silicone composition. The temperature at which 95% of the siliconepolymer is cured is also measured, typically in degrees Celsius (° C.).

Unlike the DSC results, a rheometer can reveal the physical propertiesof a material as the temperature is increased during curing. Typically,the elastic shear modulus (G′) is measured. The first derivative of theelastic modulus shows how fast the reaction is increasing. Thetemperature where the first derivative is at its greatest is a measurethe maximum reaction rate, which is approximately equivalent to the peakcure temperature obtained via DSC. The first derivative maximum,typically measured in Pascals per degree Celsius (Pa/° C.), shows themaximum rate of crosslinking and the temperature of the maximum showsthe temperature where the maximum rate occurs. The second derivative ofthe modulus curve indicates how the rate of reaction is changing. Thesecond derivative minimum temperature, generally measured in degreesCelsius (° C.) is the temperature at which the cure is nearly complete.The G′ at the second derivative minimum temperature, measured in Pascals(Pa), demonstrates the point at which the reaction has slowed to almostnear completion.

Adhesive Articles

The present disclosure also provides for adhesive articles comprising asubstrate, an adhesive applied on the substrate, and a release liner,the surface of which is layered with a cured composition. Thecomposition can be applied as a solution on a substrate or linermaterial for forming a release liner, in which the coated solution isthen cured by applying heat as disclosed herein to complete formation ofthe release liner. The present disclosure includes examples of a methodfor supplying the composition as a release layer onto the base material(e.g., a paper liner) of a release liner such as various conventionalmethods, for instance, a gravure coating method, a bar coating method, aspray coating method, a spin coating method, a knife coating method, aroll coating method, a die coating method, and the like. In someembodiments, the substrate is a label that may be made of a polymericfilm, paper, or combinations thereof. The substrate is at leastpartially covered with a thin layer of an adhesive that may be pressuresensitive. The adhesive layer is disposed between the substrate and thecured release layer of the composition.

The adhesive layer may be formed from any suitable adhesive material asdesired for a particular purpose or intended use. The adhesive layer maycomprise pressure sensitive adhesive layer, or a heat activated adhesivelayer. The pressure sensitive adhesive can be any pressure sensitiveadhesive now known in the art, for example, an acrylic adhesive, a vinylether adhesive, a polyester adhesive, a polyurethane adhesive, a rubberadhesive, a silicone adhesive, and the like or any combination thereof.In other examples, the adhesive may be any of emulsion type, solventtype, and non-solvent type, and may be either crosslinking type ornon-crosslinking type. The pressure sensitive adhesive materials thatare useful may contain as a major constituent adhesive polymersincluding, for example, acrylic type polymers, block copolymers, naturalrubber, reclaimed rubber or styrene butadiene rubbers, tackified naturalor synthetic rubbers, random copolymers of ethylene and vinyl acetate,ethylene-vinyl-acrylic terpolymers, and polyisobutylene, poly(vinylether). Typically, pressure sensitive adhesive materials are typicallycharacterized by glass transition temperatures in the range of about−70° C. to about 10° C.

In addition to the foregoing, additional components may be incorporatedinto the pressure sensitive adhesive materials. These additionalcomponents include, for example, solid tackifying resins, liquidtackifiers (e.g., plasticizers), antioxidants, fillers, pigments, waxes,etc. or a blend thereof. Particularly useful adhesives are described inU.S. Pat. Nos. 5,192,612 and 5,346,766.

The adhesive layer may have a thickness as desired for a particularpurpose or intended use. In one embodiment, the adhesive layer may havea thickness from about 10 to about 125, or from about 10 to about 75, orfrom about 10 to about 50 microns. In one embodiment, the coat weight ofthe pressure sensitive adhesive may be in the range of about 10 to about50 grams per square meter (gsm), and in one embodiment about 20 to about35 gsm.

Assembly of the adhesive layer is not limited, and may be anyappropriate assembly or configuration as needed for a particular purposeor intended use. In one embodiment, for example, the adhesive layer maycomprise a single layer, two layers, or multiple layers. In oneembodiment, the adhesive layer(s) may also be substantially continuous.In another embodiment, the adhesive layer(s) may be provided as adiscontinuous layer or layers.

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the disclosed embodimentswithout departing from the spirit and scope of the disclosure. Thus, itis intended that the present disclosure cover any and all suchmodifications and variations as come within the scope of the appendedclaims and their equivalents.

Examples

In order to exhibit the effects of specific additives on compositions, acure study was performed with compositions prepared according to Table2.

TABLE 2 20 ppm Pt catalyst, 10% CRA Silicone Base Composition usingShort Chain Linear Polymer Component Wt. % DEH 915 81.71 CRA 17 9.28 V90 7.15 HSPC 1.86

Dehesive 915 (DEH 915), the silicone base polymer, is a short-chain,linear, di-functional, vinyl-terminated silicone polymer provided byWacker Chemicals, was used for the silicone base polymer. A siliconerelease modifier resin (e.g., a controlled release agent), CRA 17, wasadded to show the compatibility between the tested additives and theother components in the release coating compositions. V90, a siliconecrosslinker provided by Wacker Chemical, and 20 ppm of HSPC (20 ppm ofplatinum atomic mass), a platinum catalyst diluted in silicone polymer,were also added to the silicone base composition.

1 pph of various additives, including acrylate cure accelerators andO-vinyl compounds, set forth below in Table 3, were added to thecomposition mixture identified in Table 2 to form a reactive mixture forcuring. The reactive compositions were cured at in a DSC at a ramp of10° C./min as previously described and the peak temperatures, peakheights, peak widths, peak areas, and temperatures at 95% cure of therelease coating composition were measured via DSC as previouslydescribed. The results obtained are also included in Table 3.

TABLE 3 Curing Study of 1 pph Additive and 20 ppm Pt catalyst, 10% CRASilicone Base Composition in DSC Peak Peak Peak Peak Temp ΔT Temp HeightWidth Area (° C.) (T95% − Additive (° C.) (W/g) (° C.) (J/g) 95% CurePeak T) Control (No Additive) 127.8 2.377 2.51 43.96 134.5 6.61 N-VinylCompounds N-Vinyl-Pyrrolidone (NVP) 150.3 0.1479 28.06 22.76 170 19.63N-Vinyl-Caprolactam (NVC) 162.3 0.3987 8.55 35.45 168.6 6.24 O-VinylCompounds 1,4 Cyclohexanedimethanol Divinyl 128.0 2.688 2.79 49.74 133.75.68 Ether Butanedioldivinylether 129.0 3.277 2.79 57.66 133.8 4.75dodecylvinylether 129.5 3.315 2.47 53.24 134.6 5.03 MethacrylatesIsobornyl Methacrylate 126.5 1.933 2.88 40.84 133.1 6.561,10-Decamethylene Glycol 127.2 1.992 2.98 43.97 134.3 7.09Dimethacrylate Isodecyl Methacrylate 129.0 2.028 2.79 42.41 135.9 6.94Methacryloxypropyl Trimethoxysilane 128.7 1.286 2.43 21.45 133.1 4.45Acrylates Hexane Diol Diacrylate (HDDA) 115.4 1.768 3.54 47.5 123.1 7.7Tricyclodecanediol Diacrylate 119.1 1.899 3.13 45.02 125.8 6.61 (Ebecryl130) Isobornyl Acrylate (IBOA) 116.3 2.052 2.92 43.3 122 5.68Octyl/Decyl Acrylate (ODA-N) 115 2.086 2.97 44.96 120.5 5.5 SiliconeDiacrylate (Ebecryl 350) 120.7 2.031 2.66 40.84 127.3 6.58 SiliconeHexaacrylate (Ebecryl 1360) 118.7 1.725 2.89 37.71 124.5 5.72 TegoRC722 - Silicone Acrylate 112.9 1.527 3.55 40.02 119.6 6.683-Aeryloxypropyl Trimethoxysilane 114.2 2.057 3.03 44.63 119.7 5.48TMPTA 117.7 1.855 3.73 57.51 125.4 7.68 Isodecyl Acrylate (IDA) 115.11.49 3.08 43.71 122.9 7.83 Propoxylated (3 mol) TMPTA 113.1 1.776 3.2748.86 120.8 7.67 Vinyl Vinyltrimethoxysilane 130.1 1.951 2.51 38.04136.3 6.11 Allyltrymethoxysilane 124.8 2.624 2.5 46.8 132.9 8.06

From Table 3, it can be readily observed that the peak cure temperaturefor acrylate monomer-containing compositions decreased by approximately7 to 15 degrees Celsius as compared to the additive-free controlcomposition. Acrylate monomer-containing compositions also reduced thepeak cure temperature more than the other compounds tested. Because theacrylate monomer-containing compositions significantly lowered the peaktemperature, it can be concluded that acrylate monomers directlycontributed to cure acceleration with the presence of a low amount ofcatalyst (20 ppm). In contrast, it is also observed in Table 3 thatN-vinyl compounds, vinyl compounds, and methacrylates did notbeneficially change peak cure temperature, and in certain instances,raised cure temperatures.

Additionally, wider and shorter exothermic peak heights were observedfor the acrylate monomer-containing compositions as compared to theadditive-free control composition. The slightly wider and shorter peaksshowed that while acrylates reduced the peak cure temperature, they madethe cure slightly more sluggish at the reduced temperature. However,while O-vinyl ethers did not reduce the peak cure temperature, theyincreased the reaction rate, as indicated by the greater peak heightswhile maintaining narrow peak areas.

In order to explore the effects of additives on compositions havinghigher concentrations of platinum catalyst, the experiment laid out inTable 3 was reproduced using the compositions according to Table 4. Thesame components were used for the composition as in Table 2. However,the amount of vinyl-terminated base polymer was reduced, and the amountof platinum was increased to 60 ppm. The amounts of silicone crosslinkerand release modifier resin were kept approximately the same.

TABLE 4 60 ppm Pt, 10% CRA Silicone Base Composition using Wacker ShortChain Linear Polymer Component Wt. % DEH 915 78.04 CRA 17 9.29 V 90 7.1HSPC 5.57

Less amount of additive was added to the compositions for this study.Specifically, 0.5 pph of various types of additives, including acrylatemonomers and O-vinyl compounds as set forth below in Table 5, were addedto the compositions to form reactive mixtures. The compositions werecured, and the peak temperatures, peak heights, peak widths, peak areas,and temperatures at 95% cure of the composition were measured via DSC aspreviously described. The results are listed in Table 5.

TABLE 5 Curing Study of 0.5 pph Additive, 60 ppm Pt, 10% CRA SiliconeBase Composition in DSC Peak Peak Peak Peak Temp ΔT Temp Height WidthArea (° C.) (T95% − Additive (° C.) (W/g) (° C.) (J/g) 95% Cure Peak T)Control (No Additive) 111.4 2.05 2.62 40.47 118.3 6.88 O-Vinyl Compounds1,4 Cyclohexanedimethanol Divinyl 110.6 2.261 2.69 44.84 117.4 6.81Ether Butanediodivinylether 108.8 3.313 2.64 56.04 112.8 4Dodecylvinylether 109.8 3.554 2.42 54.63 113.5 3.68 Acrylates HexaneDiol Diacrylate (HDDA) 95.0 1.58 3.04 44.01 100.9 5.94 Octyl/DecylAcrylate (ODA-N) 97.1 1.848 2.99 43.19 104.3 7.15 Silicone Diacrylate(Ebecryl 350) 103.0 1.82 2.71 38.82 109.7 6.68 Tego RC722 - SiliconeAcrylate 93.1 1.776 2.81 40.57 99.8 6.64 Anchorage 3-AeryloxypropylTrimethoxysilane 94.8 1.981 2.68 41.83 101.5 6.71 TMPTA 93.6 1.447 3.8454.53 100.7 7.14 Ethoxylated (3 mol) TMPTA 94.1 1.375 3.34 42.39 102.17.99 Propoxylated (3 mol) TMPTA 95.6 1.733 3.12 43.6 102.3 6.722-Ethoxyethoxy Ethyl Acrlyate 90.5 2.446 2.71 58.33 92.4 1.84 (EOEOEA)Propoxylated 2 neopentyl glycol 91.2 2.711 3.08 56.68 92.9 1.62diacrylate (PONPGDA) 2-Phenoxyethyl Acrylate 91.3 2.819 2.76 58.35 92.71.39 Ethoxylated (15 mol) TMPTA 98.6 2.479 2.73 49.56 102.1 3.58Polyethlyene Glycol 200 Diacrylate 88.6 2.491 2.98 54.69 93.7 5.1(PEG200DA) Stearyl Acrylate 93.9 1.976 2.55 47.33 97.8 3.91

It can be readily observed from Table 5 that the acrylatemonomer-containing compositions exhibited a significant decrease in peakcure temperature (e.g., approximately 8.4 to 22.9 degrees Celsius lower)as compared to the additive-free control composition. As compared to the20 ppm platinum catalyst acrylate-containing compositions studied inTable 3, the 60 ppm platinum catalyst acrylate monomer-containingcompositions showed an even more dramatic increase in peak curetemperature. Similarly, it can be seen that while O-vinyl compounds onlyreduced the peak cure temperature 0.9 to 2.7 degrees Celsius, theyincreased the peak heights while maintaining narrow peak widths. Thus,the O-vinyl compounds increasing the intensity of the cure. Thus, it canbe seen that acrylates and O-vinyl ethers affect the cure inindependent, but complementary ways.

Regarding peak area, the acrylate-containing compositions generallyexhibited larger peak area values than the additive-free controlcomposition, although the degree varied based on the type of acrylatemonomer used. Likewise, the O-vinyl compounds tested consistentlyexhibited larger peak areas and peak heights than both the acrylatemonomer-containing compositions and the additive-free controlcomposition. Accordingly, it can be concluded that the inclusion ofacrylate monomers and O-vinyl compounds can result in a greater portionof the compositions to being cured (e.g., cure enhancement).Nevertheless, the results in Table 3 and Table 5 demonstrate that thecure acceleration and enhancement generated by acrylate monomers andO-vinyl compounds occurred across a range of platinum catalystconcentrations (20 to 60 ppm) and additive amounts (0.5 to 1 pph). Thus,low amounts of cure accelerator and low amounts of catalyst can beutilized while still achieving effective cure.

In order to show that cure acceleration and cure enhancement were notlimited to the silicone base composition components used in the previousstudies, the experiment was repeated with compositions containingdifferent silicone polymers, crosslinkers, and controlled release agentsas described in Table 6. Furthermore, the compositions included a lowamount of catalyst −35 ppm of platinum catalyst, as opposed to the 20ppm and 60 ppm concentrations tested in previous studies.

TABLE 6 35 ppm Pt, 10% CRA Silicone Base Composition using Dowmultifunctional polymer Component Wt. % SL 161 81.82 SL 40 9.44 74885.59 SL 3000 3.16

SL 161, a vinyl-terminated, multifunctional silicone polymer containingvinyl groups along the polymer chain and provided by Dow Chemical, wasused for the silicone base polymer. SL 40, a silicone release modifierresin (e.g., controlled release agent), was added to show thecompatibility between the tested additives and the other components inthe release coating compositions. 7488, a silicone crosslinker providedby Wacker Chemical, and 35 ppm of SL 3000, a platinum catalyst, werealso added to the silicone base composition.

0.5 pph of various additives, as described in Table 7, were added to thesilicone base composition. The compositions were cured, and the peaktemperatures, peak heights, peak widths, peak areas, and temperatures at95% cure of the composition were measured via DSC as previouslydescribed. The results are included in Table 7.

TABLE 7 Curing Study of 0.5 pph Additive, 35 ppm Pt, 10% CRA SiliconeBase Composition in DSC Peak Peak Peak Peak Temp ΔT Temp Height WidthArea (° C.) (T95% − Additive (° C.) (W/g) (° C.) (J/g) 95% Cure Peak T)Control (No Additive) 122.7 2.004 2.87 42.39 129.0 6.31 O-VinylCompounds 1,4 Cyclohexanedimethanol Divinyl Ether 121.7 2.038 3.09 46.78129.8 8.06 Butanediodivinylether 120.5 2.094 2.88 57.79 139.3 18.87dodecylvinylether 122.2 2.082 2.75 50.73 134.6 12.4 Meth-AcrylatesSteryl Methacrylate 119.8 2.66 2.52 49.64 125.9 6.07 Acrylates HexaneDiol Diacrylate (HDDA) 105.7 1.505 3.96 48.38 115.6 9.99 IsobornylAcrylate (IBOA) 110.7 1.32 3.36 44.69 123.9 13.11 Octyl/Decyl Acrylate(ODA-N) 107.7 1.319 3.24 43.22 115.1 7.36 Silicone Hexaacrylate (Ebecryl1360) 111.9 1.725 3.24 44.6 118.7 6.85 Tego RC722 - Silicone AcrylateAnchorage 104.0 1.778 3.4 46.54 111.3 7.27 3-AeryloxypropylTrimethoxysilane 104.7 1.842 3.39 48.13 112.6 7.88 TMPTA 110.2 1.7143.92 52.23 116.4 6.2 Isodecyl Acrylate (IDA) 107.1 1.366 3.41 46.67119.7 12.54 Ethoxylated (3 mol) TMPTA 105.5 1.495 3.72 47.33 116.4 10.91Propoxylated (3 mol) TMPTA 106.9 1.643 3.71 48.85 116.8 9.892-Ethoxyethoxy Ethyl Acrlyate 102.4 1.539 3.07 49.14 106.5 4.01 (EOEOEA)Propoxylated 2 neopentyl glycol diacrylate 104.0 1.381 3.64 45.47 110.76.72 (PONPGDA) 2-Phenoxyethyl Acrylate 102.7 1.487 2.81 41.19 107.3 4.59Ethoxylated (15 mol) TMPTA 108.9 1.477 2.72 40.25 112.5 3.54Polyethlyene Glycol 200 Diacrylate 99.8 1.65 3.39 44.7 106.8 6.98(PEG200DA) Stearyl Acrylate 108.1 1.918 3.09 46.4 113.6 5.49

From Table 7, it is evident that the acrylate-containing compositionsexhibited significantly lower peak cure temperatures as compared to theadditive-free control composition. The O-vinyl compounds did not have asignificant impact on the peak cure temperature. Accordingly, it can beconcluded that the acrylate monomer's ability to accelerate the cure isindependent of the particular types of silicone polymer, crosslinker,controlled release agent, and platinum catalyst used in the siliconebase coating composition. It can be further concluded in comparing theresults of Tables 3, 5 and 7 that the acrylate monomer will acceleratethe cure independent of the amount of platinum catalyst present in thesilicone base composition.

In contrast to the additive-free control compositions, shorter and widerpeaks were observed in the acrylate monomer-containing compositions.Both the acrylate monomer-containing and O-vinyl compound-containingcompositions exhibited increased peak areas when compared to theadditive-free control composition, indicating that a greater portion ofthose silicone base compositions were cured (e.g., cure enhancement).However, the O-vinyl compounds, which generally had the larger peakheights, proved to be the most effective cure enhancers. In view ofthese results, it is evident that the cure-enhancing properties of theO-vinyl compounds and acrylate monomers are independent of theparticular amounts and types of silicone polymer, crosslinker,controlled release agent, and platinum catalyst used in the siliconebase coating composition.

To further demonstrate the cure accelerating and enhancing abilities ofacrylate monomers across silicone compositions containing varying levelsof platinum catalyst, silicone base compositions according to Table 8were prepared. SL 161 was used as the silicone base polymer and 7488 wasused as the silicone crosslinker. No controlled release agent was addedto these compositions. SL 3000, a platinum catalyst, was added to thecompositions in amounts of 10, 20, 30 and 35 ppm, respectively, as setforth below.

TABLE 8 0% CRA Silicone Base Composition using Dow multifunctionalpolymer 10 ppm 20 ppm 30 ppm 35 ppm Formula Formula Formula FormulaComponent Wt. % Wt. % Wt. % Wt. % SL 161 94.20 94.2 94.2 91.8 7488 4.944.94 4.94 4.9 SL 3000 0.91 1.83 2.75 3.3

2-Ethoxyethoxy Ethyl Acrylate (EOEOEA), an acrylate monomer, was used asthe additive and added on top of the 10 ppm, 20 ppm, and 30 ppm siliconebase compositions in amounts of 0.25, 0.5, 1, 2, 5, and 10 pph,respectively. Upon the addition of EOEOEA, the compositions were cured,and the peak temperatures, peak heights, peak widths, peak areas, andtemperatures at 95% cure were measured via DSC as previously described.The results are set forth below in Table 9.

TABLE 9 Curing Study Varying Pt and Additive (EOEOEA) Levels Peak PeakPeak Peak Temp ΔT EOEOEA Temp Height Width Area (° C.) (T95% − (pph) ppmPt (° C.) (W/g) (° C.) (J/g) 95% Cure Peak T) 0.00 (control)   10 141.01.79 2.56 35.48 146.6 5.6 0.25 10 132.1 1.555 2.87 36.34 138.2 6.09 0.510 129.4 1.036 3.22 36.18 136.7 7.25 1 10 125.9 0.9237 4.24 36.53 134.08.11 2 10 123.1 0.7773 5.22 35.31 132.5 9.41 5 10 120.1 0.6839 5.5436.53 135.0 14.93 10 10 116.3 0.7641 5.6 39.67 134.5 18.18 0 (control)20 131.5 1.979 2.35 36.69 136.9 5.35 0.25 20 118.6 1.122 2.91 32.09124.4 5.79 0.5 20 115.2 1.008 3.22 35.09 121.7 6.49 1 20 112.4 0.7524.03 36.77 119.4 7.02 2 20 110.0 0.8458 5.47 41.71 112.5 2.5 5 20 105.50.7668 5.31 41.92 121.6 16.03 10 20 101.7 0.651 6.85 41.29 119.9 18.15 0(control) 30 126.0 2.096 2.29 36.81 130.5 4.51 0.25 30 110.1 1.102 2.8234.08 115.4 5.31 0.5 30 107.3 1.181 3.37 36.69 114.6 7.24 1 30 105.31.075 4.3 41.65 115.4 10.15 2 30 102.2 0.8317 5.91 42.64 114.1 11.91 530 96.0 0.8392 5.23 49.97 120.2 24.22 10 30 91.9 0.6329 7.45 49.39 113.821.88

As is evident from Table 9, the EOEOEA-containing compositions at eachplatinum concentration exhibited a substantial decrease in peak curetemperature, and experienced an accelerated cure. Perhaps moresignificantly, the amount of acrylate monomer required to achieve themost pronounced cure acceleration can be determined from Table 9. Asshown in FIG. 1 , the steepest reduction in peak cure temperatureoccurred when between about 0.25 and about 2 pph of EOEOEA were added tothe base composition across the various platinum-containingconcentrations. While the addition of acrylate monomer in amountsgreater than about 2 pph also resulted in decreased peak temperature,the reduction was not as pronounced. Thus, it can be concluded that themost pronounced cure acceleration is observed when about 2 pph or lessof acrylate monomer is added to a silicone base composition prior tocure, and irrespective of the composition's platinum concentration asevidenced by the Examples.

Similarly, as shown in FIG. 2 , the peak width drastically increasedwhen between about 0.25 and about 2 pph EOEOEA was added to the variousplatinum-containing compositions. However, the change in peak widthgenerally remained constant when between about 2 and about 10 pph EOEOEAwas added to the compositions. Accordingly, FIG. 2 also demonstratesthat the most pronounced cure acceleration occurs when about 2 pph orless of acrylate monomer is added to the silicone base compositions,irrespective of the composition's platinum concentration.

In order to demonstrate that about 2 pph or less of acrylate monomerproduces the most pronounced cure acceleration across a range ofacrylate monomers and platinum catalyst concentrations, additionalacrylate monomers were studied in various amounts in silicone basecompositions containing higher concentrations of platinum catalyst. Twoacrylate monomers, Octyl/Decyl Acrylate (ODA) and Tego RC722-SiliconeAcrylate Anchorage (Tego RC722), were added to the 35 ppm silicone basecomposition set forth above in Table 8. The acrylate monomers were addedin amounts of 0.1, 0.2, 0.5, 1, 2, 5, and 10 pph, respectively, on topof the silicone base composition. Upon the addition of the acrylatemonomers, the compositions were cured as previously described and thepeak temperatures, peak heights, peak widths, peak areas, andtemperatures at 95% cure were measured via DSC. The results are setforth below in Tables 10 and 11, respectively.

TABLE 10 Curing Study Varying Additive Level Using ODA and 35 ppm PtCatalyst-containing Silicone Base Composition Peak Peak Peak Peak TempΔT ODA Temp Height Width Area (° C.) (T95% − (pph) (° C.) (W/g) (° C.)(J/g) 95% Cure Peak T) 0 (control) 122.7 2.004 2.87 42.39 129.0 6.31 0.1113.6 2.173 2.86 50.98 120.4 6.8 0.2 110 2.214 2.87 48.95 116.3 6.37 0.5106.7 2.458 3.13 59.05 114.7 7.95 1 105.6 2.184 3.53 58.58 114.7 9.04 2103.2 1.253 4.69 53.46 134.7 31.48 5 103.0 1.413 4.98 67.28 126.9 23.9510 104.3 1.212 5.96 70.12 139.1 34.87

TABLE 11 Curing Study Varying Additive Level Using Tego RC722 and 35 ppmPt Catalyst-containing Silicone Base Composition Peak Peak Peak PeakTemp ΔT Tego Temp Height Width Area (° C.) (T95% − (pph) (° C.) (W/g) (°C.) (J/g) 95% Cure Peak T) 0 (control) 140.8 2.783 2.71 56.15 145.3 4.50.1 140.6 1.425 2.9 41.86 146.0 5.45 0.2 130.9 2.234 3 51.33 137.7 6.820.5 128.5 1.304 3.34 42.54 135.7 7.23 1 130.0 1.16 3.41 42.35 138.4 8.352 126.2 0.9962 3.88 44.61 135.1 8.96 5 126.9 0.9172 6.78 51.61 144.117.22 10 130.3 0.4899 12.06 47.18 153.7 23.38

As demonstrated by the reduced peak cure temperatures shown in Tables 10and 11, the acrylate-containing compositions exhibited accelerated cures(e.g., reduced peak temperatures) when compared to the acrylate-freecontrol composition. The peak cure temperatures in Tables 10 and 11 wereplotted against the amounts of acrylate in order to generate FIGS. 3 and4 , respectively. Both FIG. 3 and FIG. 4 show a sharp decrease in peakcure temperature for the compositions containing ODA and Tego RC722 inamounts of about 2 pph or less, for example, when an acrylate cureaccelerator is added in an amount of about 0.2 to about 2 pph or wt %.The addition of more than about 2 pph of the acrylate cure acceleratordid not reduce the temperature as dramatically but was neverthelesseffective. Accordingly, it can be concluded that the addition of about 2pph or less (e.g., about 0.1 or about 0.2 to about 2 pph) of acrylatemonomer as a cure accelerator to a silicone base composition generates apronounced decrease in peak cure temperature, and that this range isgenerally the most effective for all acrylate monomers irrespective ofthe composition's platinum concentration, which can be about 60 ppm orless, about 50 ppm or less, about 40 ppm or less, or about 35 ppm orless.

The above studies focused on the addition on a single type of additiveto a silicone base composition. Accordingly, a study was performed byadding two additives to a silicone base composition, namely one acrylatemonomer and one O-vinyl compound. The 10 ppm, 20 ppm, and 30 ppmsilicone base compositions set forth in Table 8, above, were used forthis study. One acrylate monomer (TMPTA) and one O-vinyl compound (BDVE)were added on top of the silicone base compositions in the amountsindicated in Table 12. Upon the addition of the TMPTA and BDVE, thecompositions were cured, and the peak temperatures, peak heights, peakwidths, peak areas, and temperatures at 95% cure were measured via DSCas previously described. The results are set forth in Table 12.

TABLE 12 Cure Study Using One Acrylate Additive (TMPTA) and One VinylEther Additive (BDVE) With Silicone Base Compositions Containing VaryingPt Levels Peak Peak Peak Peak Temp ΔT Pt TMPTA BDVE Temp Height WidthArea (° C.) (T95% − (ppm) (pph) (pph) (° C.) (W/g) (° C.) (J/g) 95% CurePeak T) 10 (control) 0 0 140.9 0.8102 2.49 28.34 146.0 5.13 10 0 0.5141.8 1.198 3.19 35.03 148.9 7.12 10 0.25 0.25 129.0 1.02 3.98 36.58137.4 8.44 10 0.5 0 130.0 1.176 3.96 39.52 137.8 7.77 10 0.5 0.5 127.31.184 4.18 43.04 138.8 11.47 20 0 0.25 130.2 1.843 2.73 38.97 136.5 6.2920 0.25 0 116.7 1.234 3.42 34.13 122.9 6.24 20 0.25 0.25 116.5 1.2723.68 38.75 123.9 7.32 20 0.25 0.25 115.8 1.268 3.68 39.1 123.5 7.65 200.25 0.25 116.4 1.355 3.56 39.65 123.9 7.48 20 0.25 0.25 117.1 1.16 3.6138.28 125.0 7.90 20 0.25 0.25 118 1.257 3.67 39.46 124.8 6.86 20 0.250.25 115.6 1.375 3.5 39.51 123.1 7.48 20 0.25 0.5 115.6 1.28 3.97 42.28123.7 8.12 20 0.5 0.25 115.4 0.769 4.88 39.82 127.3 11.94 30 (control) 00 126.9 1.543 2.56 34.43 133.2 6.34 30 0 0.5 123.5 1.412 2.31 30.12127.5 4.05 30 0.25 0.25 109.3 1.294 3.71 40.07 116.6 7.30 30 0.5 0 110.91.267 3.79 40.7 118.9 8.01 30 0.5 0.5 107.8 0.9201 4.54 40.77 119.211.39

Table 12 shows that the combination of an acrylate monomer (TMPTA) andan O-vinyl compound (BDVE) resulted in significantly reduced peak curetemperatures when compared to the additive-free control compositions,the acrylate monomer-containing composition, and the o-vinylcompound-containing composition. Because the compositions containing theacrylate monomer/O-vinyl compound bend reduced the peak cure temperaturethe most, it can be concluded that the acrylate monomer/O-vinyl compoundblend is an effective cure accelerator combination.

Similarly, compositions containing both an acrylate monomer and anO-vinyl compound exhibited the largest peak areas while maintaining peakheight and reaction rate, which indicates that a greater portion ofthose compositions were cured (e.g., cure enhancement) than theadditive-free compositions, the acrylate monomer-containingcompositions, and the O-vinyl compound-containing compositions.Accordingly, it can be concluded that the acrylate monomer/O-vinylcompound blend is also an effective cure enhancer.

In order to evaluate the potential effect of acrylate monomer on theelasticity of a cured silicone base composition, a study was performedvia rheometer using the silicone base composition containing 10 ppm ofplatinum catalyst set forth above in Table 8. 0.25 pph of additives, asset forth below in Table 13, were added to the base composition. Oncethe additive was incorporated, the composition was cured as previouslydescribed and the first derivative maximum temperature, first derivativemaximum reaction rate, second derivative minimum temperature, and G′ atthe second derivative minimum temperature values were obtained using arheometer. The results are reflected below in Table 13.

TABLE 13 Cure Study Using 10 ppm Pt catalyst, 0% CRA Silicone BaseComposition and 0.25 pph of Additive in Rheometer First First Second G′at the Derivative Derivative Derivative second Max. Max. Reaction Min.derivative min. Additive Temp. (° C.) Rate (Pa/° C.) Temp.(° C.) temp.(Pa) None (Control) 131.7 115938 139.8 1485930 Stearyl 133.0 116936138.1 1320490 methacrylate 2(2-Ethoxyethoxy)-ethyl 125.2 110245 130.51298830 acrylate ODA-N 128.6 102195 133.2 1442760 Propoxylated (3 mol)121.8 111283 130.0 1417390 trimethylolpropane triacrylate (TMPTA) TMPTA126.0 119646 130.1 1431930 Polyethylene glycol (200) 123.5 110998 131.11531190 diacrylate

As evidenced by the G′ at the second derivative minimum temperaturevalues for the acrylate monomer-containing compositions and theacrylate-free control composition in Table 13, the acrylate monomergenerally does not appear to significantly affect the elasticity of thecured composition.

Finally, in order to evaluate the effects of acrylate and O-vinylcompounds on the elasticity of a cured composition, a cure study wasperformed via rheometer on silicone base compositions containing noadditives (control), only acrylate monomer, and a blend of acrylatemonomer and o-vinyl compound. 0.25 pph of the acrylate monomer TMPTA wasadded on top of a 30 ppm platinum catalyst silicone base composition asset forth in Table 8. Similarly, 0.25 pph TMPTA and 0.2 pph of theo-vinyl ether, BDVE, were added on top of another 30 ppm platinumcatalyst silicone base composition as set forth in Table 8. These twosamples, in addition to one sample containing no additive (control),were subjected to curing as previously described. The storage modulusvalues were measured via rheometer as the temperature was continuouslyincreased by 10° C./min. The data obtained is reflected below in Table14 and in FIG. 5 .

TABLE 14 Cure Study of 30 ppm Pt, 0% CRA Silicone Base Compositions withNo Additives, Acrylate Monomer, and Acrylate Monomer/O-Vinyl Compound inRheometer 30 ppm Pt, no additive 30 ppm Pt 0.25 pph TMPTA, (control) 30ppm Pt 0.25 pph TMPTA 0.2 pph BDVE Storage Storage Storage Temperaturemodulus (G′) Temperature modulus (G′) Temperature modulus (G′) (° C.)(Pa) (° C.) (Pa) (° C.) (Pa) 70.6 −1.77846 70.6 −3.84436 70.7 1.273972.3 1.30734 72.2 −1.35743 72.3 −1.73367 73.8 0.586421 73.8 3.08266 73.81.5806 75.4 0.45179 75.4 −2.78624 75.5 −0.871981 76.9 −3.50808 76.91.20316 77.0 −4.93409 78.5 1.20395 78.5 −1.85207 78.6 1.41169 80.10.772929 80.1 −2.29559 80.2 2.25611 81.6 −0.542157 81.6 2.49473 81.71.02462 83.3 −2.03659 83.3 −0.711701 83.3 −1.88941 84.8 2.2238 84.8−1.34018 84.9 −0.978462 86.4 1.36033 86.3 −1.87138 86.5 3.93045 87.94.51172 87.9 1.23201 88.1 −0.43879 89.5 10.9115 89.5 1.81252 89.60.697698 91.1 37.7744 91.1 2.11179 91.2 −1.13305 92.7 90.4595 92.72.45116 92.7 −1.99146 94.3 175.694 94.3 41.7441 94.3 −2.37431 96.3451.734 96.5 761.26 96.3 0.5568 98.4 904.776 98.2 3335.71 97.9 26.9072100.7 1651.19 100.1 13297.8 104.8 263655 102.4 2389.19 101.9 51220.8107.1 545407 103.9 3436.19 105.4 257922 110.1 999929 106.4 26777.3 109.3810975 112.2 1331950 108.5 60594.1 111.4 1103820 114.9 1562680 110.494585.2 113.5 1355620 117.3 1614690 113.1 200071 116.0 1454660 119.51643060 115.6 301467 118.1 1484570 121.8 1668450 118.0 573494 120.71510770 124.3 1693650 120.9 1062510 123.2 1533160 126.9 1718610 123.51314750 125.6 1554890 129.2 1740470 126.2 1454020 128.0 1575920 131.71764710 128.5 1497610 130.6 1597330 133.9 1785790 130.9 1518300 133.11618300 136.4 1809210 133.3 1537480 136.6 1651960 138.7 1830810 135.61555480 138.7 1666210 141.1 1852660 137.8 1573300 141.1 1686390 143.51876040 140.2 1592540 143.5 1707460 145.9 1898340 142.5 1610460 145.91726250 148.4 1921200 144.9 1629930 148.2 1746230 150.7 1942910 147.51649650 150.5 1766540 153.0 1963840 149.9 1668920 153.0 1787340 155.11984900 152.4 1688180 155.5 1807790 157.7 2008230 154.8 1707430 157.91828680 160.1 2030600 157.4 1727390 160.3 1848930 162.5 2052880 159.71745840 162.7 1869140 164.9 2075530 162.1 1764950 165.2 1889760 167.32098330 164.7 1785300 167.5 1909260 169.6 2119440 167.1 1804290 169.91930290 172.0 2142180 169.6 1824060 172.4 1950870 174.4 2164740 171.91842990 174.7 1970580 176.6 2186170 174.5 1863090 177.1 1990210 178.92207400 177.1 1883960 179.6 2012180 180.5 2220620 179.5 1903480 180.52012080 180.5 1908060

As shown in FIG. 5 , the TMPTA-only and TMPTA/BDVE-containingcompositions attained peak cure temperatures at approximately 10 and 13degrees Celsius lower, respectively, than the additive-free composition.This indicates that the TMPTA-only and TMPTA/BDVE-containingcompositions exhibited an accelerated rate of cure, with theTMPTA/BDVE-containing composition curing slightly faster. Furthermore,the TMPTA-only and TMPTA/BDVE-containing compositions also achievedhigher storage moduli values than the additive-free composition, withthe TMPTA/BDVE-containing composition exhibited the highest storagemoduli value. Thus, it is evidenced that the use of acrylate monomers,O-vinyl compounds, or blends thereof does not negatively impact theelasticity of a cured silicone base composition.

In order to exhibit applying the compositions of the present disclosureon a flexible liner and forming a release liner, in addition to formingan adhesive article, compositions were formed from the followingcomponents listed in Tables 15-19.

TABLE 15 Composition 1 Component Wt. % DEH 915 80.26 CRA 17 9.6 V 907.17 HSPC 2.77 Cure accelerator 0.2

Dehesive 915 (DEH 915), the silicone base polymer, is a short-chain,linear, di-functional, vinyl-terminated silicone polymer provided byWacker Chemicals, was used for the silicone base polymer. A V90, asilicone crosslinker provided by Wacker Chemical, was added and mixeduntil uniform. The silicone crosslinker is an organo-hydrogenpolysiloxane having at least an average of two or more siliconatom-bound hydrogen atoms (Si—H groups) within one molecule: an amountsuch that the number of moles of the Si—H groups is equal to 1 to 5times that of the number of moles of the alkenyl groups within thesilicone base polymer. A silicone release modifier resin (e.g., acontrolled release agent), CRA 17, was added to the silicone basepolymer and agitated until uniform. The platinum solution, Wacker HSPC,was used to bring the ppm of platinum to 30 ppm in terms of platinumatomic mass. Lastly, 0.2 parts by mass of 3-AcryloxypropylTrimethoxysilane as an acrylate cure accelerator is added to the mixtureand mixed for 10 minutes.

As a first control composition, the components listed in Table 16 werecombined.

TABLE 16 Control Composition 1 Component Wt. % DEH 915 77.54 CRA 17 9.29V 90 7.1 HSPC 5.57 Cure accelerator 0.5

Dehesive 915 (DEH 915), the silicone base polymer, is a short-chain,linear, di-functional, vinyl-terminated silicone polymer provided byWacker Chemicals, was used for the silicone base polymer. A V90, asilicone crosslinker provided by Wacker Chemical, was added and mixeduntil uniform. A silicone release modifier resin (e.g., a controlledrelease agent), CRA 17, was added to the silicone base polymer andagitated until uniform. The platinum solution, Wacker HSPC, was used tobring the ppm of platinum up to 60 ppm in terms of platinum atomic mass.Lastly, 0.5 parts by mass of Vinyltrimethoxysilane as a cure acceleratoris added to the mixture and mixed for 10 minutes.

As a second control composition, the components listed in Table 17 werecombined.

TABLE 17 Control Composition 2 Component Wt. % DEH 915 77.54 CRA 17 9.29V 90 7.1 HSPC 5.57 Cure accelerator 0.5

Dehesive 915 (DEH 915), the silicone base polymer, is a short-chain,linear, di-functional, vinyl-terminated silicone polymer provided byWacker Chemicals, was used for the silicone base polymer. A V90, asilicone crosslinker provided by Wacker Chemical, was added and mixeduntil uniform. A silicone release modifier resin (e.g., a controlledrelease agent), CRA 17, was added to the silicone base polymer andagitated until uniform. The platinum solution, Wacker HSPC, was used tobring the ppm of platinum up to 15 ppm in terms of platinum atomic mass.Lastly, 0.5 parts by mass of Vinyltrimethoxysilane as a cure acceleratoris added to the mixture and mixed for 10 minutes.

As another example composition, excluding a controlled release agent,the components listed in Table 18 were combined.

TABLE 18 Composition 2 Component Wt. % SL 161 93.16 7488 5.23 SL 30001.37 Cure accelerator 0.25

Dow silicone SL 161 was used for the silicone base polymer. A 7488, asilicone crosslinker provided by Dow, was added and mixed until uniform.The platinum solution, SL 3000, was used to bring the ppm of platinum to15 ppm in terms of platinum atomic mass. Lastly, 0.25 parts by mass ofTMPTA, trimethylolpropane triacrylate, as a cure accelerator is added tothe mixture and mixed for 10 minutes.

As another example composition, excluding a controlled release agent,the components listed in Table 19 were combined.

TABLE 19 Composition 3 Component Wt. % SL 161 93.16 7488 5.23 SL 30001.37 Cure accelerator 0.25

Dow silicone SL 161 was used for the silicone base polymer. A 7488, asilicone crosslinker provided by Dow, was added and mixed until uniform.The platinum solution, SL 3000, was used to bring the ppm of platinum to15 ppm in terms of platinum atomic mass. Lastly, 0.25 parts by mass ofpropoxylated (3 mol) TMPTA, trimethylolpropane triacrylate, as a cureaccelerator is added to the mixture and mixed for 10 minutes.

As another example composition, excluding a controlled release agent,the components listed in Table 20 were combined.

TABLE 20 Composition 4 Component Wt. % SL 161 93.16 7488 5.23 SL 30001.37 Cure accelerator 0.25

Dow silicone SL 161 was used for the silicone base polymer. A 7488, asilicone crosslinker provided by Dow, was added and mixed until uniform.The platinum solution, SL 3000, was used to bring the ppm of platinum to15 ppm in terms of platinum atomic mass. Lastly, 0.25 parts by mass ofpolyethylene glycol 200 diacrylate (PEG200DA) as a cure accelerator isadded to the mixture and mixed for 10 minutes.

As another example composition, excluding a controlled release agent,the components listed in Table 21 were combined.

TABLE 21 Composition 5 Component Wt. % SL 161 93.11 7488 5.22 SL 30001.37 Cure accelerator 0.25 Dodecyl Vinyl Ether 0.15

Dow silicone SL 161 was used for the silicone base polymer. A 7488, asilicone crosslinker provided by Dow, was added and mixed until uniform.The platinum solution, SL 3000, was used to bring the ppm of platinum to15 ppm in terms of platinum atomic mass. 0.25 parts by mass of3-Acryloxypropyl Trimethoxysilane as an acrylate cure accelerator and0.05 parts by mass of Dodecyl Vinyl Ether are added to the mixture andmixed for 10 minutes.

The control compositions of Tables 16 and 17, and compositions 1-5 asnoted in Tables 15 and 18-21 were used to coat a flexible liner with arelease layer and cured to form a release liner.

200 lbs of the control composition and compositions 1-4 were preparedand transferred into a container. The composition solution in thecontainer was coated as a release layer on kraft paper using a 5-rollsilicone coater. The coated paper was passed through three 20-foot ovenswith the temperature of the ramping from 265° F. up to 330° F. at a rateof 1850 ft./min. This creates an exit web temperature of 310° F. withabout 2 seconds of oven dwell time for the purpose of curing thecomposition of the release layer to for a release liner. The cured,coated paper was remoisturized with two steam foils to bring the paper'smoisture levels back to pre-oven levels.

The release liners formed with each composition coating were used toform an adhesive article. Using a slot die coater, the release liner wascoated with a rubber-based hot melt adhesive material. A thermaltransfer paper facestock was then laminated to the adhesive-coatedsurface of the construct to form an adhesive article.

In other examples, 100 lbs. of the control composition and compositions1-5 were prepared and placed into a container. The composition solutionin the container was coated as a release layer on kraft paper using a3-roll gravure silicone coating head. The coated paper was passedthrough three 20-foot ovens at two test speeds of 750 ft/min (for thecontrol composition and compositions 1, 3 and 4) and 1,000 ft/min (forthe control composition and compositions 1-5). The temperature of thecoated paper after the passing through the ovens was 290° F. with a 4.8seconds and 3.6 seconds of oven dwell time for test speeds 750 ft/minand 1,000 ft/min, respectively, for the purpose of curing thecomposition of the release layer to for a release liner. The releaseliners formed with each composition coating were used to form anadhesive article. The release layer side of the release liner was coatedwith an all-temp acrylic emulsion adhesive and dried in additional ovenA thermal transfer paper facestock was then laminated to theadhesive-coated surface of the construct to form an adhesive article.

In order to test for silicone extractables, samples of each of therelease liners containing the control composition and compositions 1-5were delaminated from the adhesive and facestock and the residualsilicone coat weight remaining on the paper facestock was measured usingan Oxford LabX 3500 device. The known coating weight samples of therelease liners were placed in 30 ml of MIBK or Toluene and agitated for30 minutes. The known coat weight samples of release liners were driedin a fume hood and coat weight of each sample was remeasured. Thedifference between original coating weight of the release liner and thedelaminated samples was compared to determine the amount of compositionfrom the coating of the release liner was transferred to the paperfacestock of the adhesive article. Also, the MIBK or Toluene solutionwas tested for atomic absorption of silicone.

In order to test for 32 fpm release force, 16″×2″ on the full laminateis cut. Sample is held in place on a I Mass Slip/Peel Tester TL-2300 anddelaminated at 32 fpm. This same procedure is used to measure 950 fpmrelease force but a IMASS ZPE-1100W machine is used in lieu on the IMass Slip/Peel Tester TL-2300

For measuring silicone anchorage. A sample is measure for silicone coatweight using an Oxford LabX 3500, this sample is placed under 10 lbs. offorce and rub along a felt surface for 2 ft. at a rate of 24 fpm. Thesample is then remeasured for coat weight and the ratio of silicone coatweight before and after abrasion is reported as the silicone anchoragepercentage.

The measured test data for the adhesive articles containing the releaselayer formed by the Control Composition 1 and Compositions 1-4 in theoven with a speed of 1850 ft./min is shown below in Tables 22 and 23.

TABLE 22 Platinum Silicon Coat 7-day, 32 14-day, 32 28-day, 32Concentration Weight fpm, Release fpm, Release fpm, Release Composition(ppm) (Lbs/ream) Force (g/in.²) Force (g/in.²) Force (g/in.²) Control 601.02 14.25 16.0 18.0 Composition 1 Composition 1 30 1.01 14.25 20.6321.63 Composition 2 15 1.11 12 13 14.88 Composition 3 15 1.12 11 12.512.38 Composition 4 15 1.13 9.5 11.5 11.13

TABLE 23 7-day, 950 14-day, 950 28-day, 950 Silicone fpm, Release fpm,Release fpm, Release % Silicone Anchorage Composition Force (g/in.²)Force (g/in.²) Force (g/in.²) Extractables (% Retention) Control 80.2595.63 75.0 3.3 57.52 Composition 1 Composition 1 83.0 119.81 85.58 6.4369.04 Composition 2 167 149.5 116.88 9 84 Composition 3 174 163 149.5 1173 Composition 4 160.5 159 138.38 14 65

As shown in Tables 22 and 23, Compositions 1-4, with half of theplatinum concentration (Composition 1) and a quarter of the platinumconcentration (Compositions 2-4) of the Control Composition 1, exhibitedcomparable, and sometimes improved, adhesion force to the paperfacestock. The acrylate additives in Compositions 1-4 required 50 to 75%less catalyst to achieve sufficient adhesion to the paper facestock,which acknowledges an improved savings in catalyst material.

Compositions 1-4 also exhibited an adequate percentage of siliconeextractables which indicates that the compositions cured even with asignificantly reduced amount of catalyst as compared to ControlComposition 1. As shown in Table 23, Compositions 1-4 with 30 ppm orless of catalyst were measured to have 14% or less siliconeextractables. The sufficient cure of Compositions 1-4 was furtherevidenced by all of the compositions having a greater silicone anchoragethan Control Composition 1. As shown in Table 23, Compositions 1-4 with30 ppm or less of catalyst were measured to have a silicone anchorage of60% or more, or 65% or more.

The measured test data for the adhesive articles containing the releaselayer formed by the Control Composition 2 and Compositions 1, 3 and 4 inthe oven with a speed of 750 ft./min is shown below in Tables 24 and 25.

TABLE 24 Platinum Silicon Coat Off Coater, 7-day, 32 7-day, 950Concentration Weight 32 fpm, Release fpm, Release fpm, ReleaseComposition (ppm) (Lbs/ream) Force (g/in.²) Force (g/in.²) Force(g/in.²) Control 15 0.96 — 20 167 Composition 2 Composition 1 30 0.9510.0 21 207 Composition 3 15 1.01 16.0 26 222 Composition 4 15 1.00 12.022 207

TABLE 25 Silicone Anchorage Composition % Silicone Extractables (%Retention) Control Composition 2 20.4 70.46 Composition 1 12.4 83.17Composition 3 5.5 89.83 Composition 4 6.6 87.2

As shown in Table 24, Compositions 1 and 3-4 exhibited improved adhesionforce over a range of delamination speeds to the paper facestock ascompared to Control Composition 2 without an acrylate additive. Thus,the acrylate additive contributes enhanced adhesion force performancewithout the need for additional catalyst.

Compositions 1 and 3-4 also exhibited an adequate percentage of siliconeextractables as compared to Control Composition 2, which indicates thatthe compositions cured even with a significantly reduced amount ofcatalyst. Control Composition 2 exhibited reduced cure with a measuredsilicone extractables of 20.4% as compared to the compositions withacrylate additive and the same or similar catalyst loading. As shown inTable 25, Compositions 1 and 3-4 with 30 ppm or less of catalyst weremeasured to have 12.4% or less silicone extractables, and Compositions 3and 4 had 7% or less silicone extractables. Thus, Compositions 1 and 3-4exhibited improved cure as compared to Control Composition 2 without anacrylate additive. The sufficient cure of Compositions 1 and 3-4 wasfurther evidenced by all of the compositions having a greater siliconeanchorage than Control Composition 2. As shown in Table 25, Compositions1 and 3-4 with 30 ppm or less of catalyst were measured to have asilicone anchorage of 70% or more, or 80% or more.

The measured test data for the adhesive articles containing the releaselayer formed by the Control Composition 2 and Compositions 1-5 in theoven with a speed of 1000 ft./min is shown below in Tables 26 and 27.

TABLE 26 Platinum Silicon Coat Off Coater, 7-day, 32 7-day, 950Concentration Weight 32 fpm, Release fpm, Release fpm, ReleaseComposition (ppm) (Lbs/ream) Force (g/in.²) Force (g/in.²) Force(g/in.²) Control 15 0.93 15.00 29 182 Composition 2 Composition 1 300.95 17.25 17 212 Composition 2 15 0.98 12.25 24 205 Composition 3 151.01 15.50 46 312 Composition 4 15 1.00 11.75 25 215 Composition 5 151.01 13.50 22 200

TABLE 27 Silicone Anchorage Composition % Silicone Extractables (%Retention) Control Composition 2 41.6 50.04 Composition 1 28.6 61.27Composition 2 13 72.13 Composition 3 13 71.04 Composition 4 14.8 64.03Composition 5 23 57.53

As shown in Table 26, Compositions 1-5 exhibited either comparable orimproved adhesion force over a range of delamination speeds to the paperfacestock as compared to Control Composition 2 without an acrylateadditive. Thus, the acrylate additive contributes to provide acceptableadhesion or enhanced adhesion force performance without the need foradditional catalyst.

Compositions 1-5 also exhibited an adequate percentage of siliconeextractables as compared to Control Composition 2, which indicates thatthe compositions cured even with a significantly reduced amount ofcatalyst. Control Composition 2 exhibited a significantly reduced andpoor cure with a measured silicone extractables of 41.6%. As shown inTable 27, Compositions 2-4 with 15 ppm of platinum catalyst weremeasured to have 14.8% or less silicone extractables, and Compositions 2and 3 had 13% or less silicone extractables. Thus, Compositions 2-4exhibited improved cure as compared to Control Composition 2 without anacrylate additive. The sufficient cure of Compositions 1-5 was furtherevidenced by all of the compositions having a greater silicone anchoragethan Control Composition 2. As shown in Table 27, Compositions 2 and 3with 15 ppm of platinum catalyst were measured to have a siliconeanchorage of 70% or more.

What is claimed is:
 1. An adhesive article comprising: a) a substrate;b) an adhesive disposed on the substrate; c) a release liner ofcomprising a first surface; d) a cured form of a composition disposed ona portion of the first surface of the liner, the cured form of acomposition comprising: i. a silicone base polymer; ii. an acrylate cureaccelerator present in an amount between about 0.05 to about 1 wt. %based on the total weight of the composition; iii. a catalyst present inthe range of between about 10 ppm to about 40 ppm of the total weight ofthe composition, wherein after exposing the composition to a temperaturein the range of 90° C. to about 120° C. for a time period in the rangeof about 2 seconds to about 8 seconds, the composition is cured 95% ormore to form the cured form of the composition, wherein the curedcomposition of the release liner is in contact with the adhesive.
 2. Theadhesive article of claim 1, wherein the silicone base polymer is avinyl functional silicone base polymer.
 3. The adhesive article of claim1, wherein the silicone base polymer is present from between about 50wt. % to about 95 wt. % of the total weight of the composition.
 4. Theadhesive article of claim 1, further comprising an O-vinyl ethercompound.
 5. The adhesive article of claim 4, wherein the O-vinyl ethercompound is selected from the group consisting of 1,4cyclohexanedimethanol divinyl ether, butanedioldivinylether, anddodecylvinylether.
 6. The adhesive article of claim 4, wherein theO-vinyl ether compound is present from between about 0.01 wt. % to about10 wt. % of the total weight of the composition.
 7. The adhesive articleof claim 1, wherein the acrylate cure accelerator is selected from thegroup consisting of a mono-, di-, tri-, and multifunctional acrylate. 8.The adhesive article of claim 7, wherein the acrylate cure acceleratoris selected from the group consisting of hexane diol diacrylate,tricyclodecanediol diacrylate, isobornyl acrylate, octyl/decyl acrylate,silicone diacrylate, silicone hexaacrylate, 3-acryloxypropyltrimethoxysilane, and trimethylolpropane triacrylate.
 9. The adhesivearticle of claim 1, wherein the acrylate cure accelerator is ahydrophilic acrylate monomer.
 10. The adhesive article of claim 1,further comprising a crosslinking agent comprising a silicone hydridefunctional group.
 11. The adhesive article of claim 1, furthercomprising a controlled release agent, the controlled release agent ispresent in an amount of less than 50 wt. % of the total weight of thecomposition.
 12. The adhesive article of claim 1, wherein the catalystcomprises platinum.
 13. The adhesive article of claim 12, wherein thecatalyst is present at about 35 ppm or less of the total weight of thecomposition.
 14. The adhesive article of claim 1, wherein the timeperiod for curing the composition is in the range of about 1 second toabout 5 seconds and the temperature for curing the composition is in therange of about 100° C. to about 130115° C.
 15. The adhesive article ofclaim 1, wherein the modulus (G′) of the composition after curing is1×10⁶ Pascals or more measured at a temperature of about 120° C. andwherein the loss factor (tan.delta.) of the composition after curing isless than 0.01 measured at a temperature of about 120° C.
 16. Theadhesive article of claim 1, wherein the acrylate cure accelerator isthe sole cure accelerator present in the composition.
 17. The adhesivearticle of claim 1, wherein the liner is selected from the groupconsisting of a polymer film, a plastic film, and a paper liner.
 18. Theadhesive article of claim 1, wherein the substrate is selected from thegroup consisting of a polymeric film, paper, and combinations thereof.19. The adhesive article of claim 1, wherein the adhesive is a pressuresensitive adhesive.
 20. The adhesive article of claim 1, wherein theacrylate cure accelerator is a mono-functional acrylate cureaccelerator.